Review Draw a model of each of the hydrogen isotopes -Hydrogen-1 -Hydrogen-2 -Hydrogen-3.
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Hydrogen storage, distribution and infrastructure
Dr.-Ing. Roland Hamelmann D-23611 Bad Schwartau
1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
Hydrogen storage Storage principles Example
Gas - CNG, Pressure vessels
Fluid - Cryo tanks
Physically bound - Metal hydride storage, C-fibre
Chemichally bound - Sodiumborhydride, Ammonia
Criteria
Gravimetric density [kWh/kg] - Weight limited applications
Volumetric density [kWh/m³] - Volume limited applications
Safety - Duty, accident
Efficiency - Energetic effort for in- and output
Application - Mobile/stationary - continous / discontinous - heat coupling
1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
Identical with CNG-storage
Large storages (> 106 Nm³ ): Aquifere, Kavernen • England: saline caverns for hydrogen storage (ICI) with 50 bar • France (57-74): Aquifer-storage for für 330 Mio Nm³ town gas (50 % H2)
Small storages: sperical pressure vessels • Low pressure sphere (1,4 MPa, 15.000 Nm³, D=29m) • Cylinder (D = 2,8 m, H = 7,3/10,8/19 m, 1305/2250/4500 Nm³ volume @ 4,5 MPa) • Steel bottles (2-50 dm³): 8,3 Nm³ volume @ 20 MPa, 50 dm³; 11,8 Nm³ volume @ 30 MPa
Stationary storages
Saline caverns
Source: KBB Underground
Cavern building
Source: KBB Underground
Source: Wasserstoff, Info-Blatt Messer Griesheim
Pressure vessels
Hydrogen storage density
Ideal gas: p*V = m*R*T Real gas: p*V = Z*m*R*T
p: pressure V: volume m: mass R: gas constant T: temperature Z: compressibility factor
Example: energy content of a gasholder (V1 = 100 m³, p1 = 250 bar, T1 = 300 K) 1) Standard volume V2 = V1 * p1/p2 * T2/T1 * Z2/Z1
= 100 m³ * 250 * 300/293 * 1/1,142 = 22.414 m³
2) Energy content E = Hi * V = 3,0 kWh/m³ * 22.414 m³ = 67.243 kWh = 67, 2 MWh
3) Electrical equivalent Eel = E * η ≈ 67,2 MWh * 40 % = 26,9 Mwhel
4) Storage density ds = 26,9 Mwhel / 100 m³ = 269 kWhel / m³
Source: Funck, Handbook of Fuel Cells Vol 3, S. 83 (2003)
Similar to pressure tanks for CNG-mobility
Composite tanks are 50-75 % easier than steel (carbon-fibre reinforced aluminium or plastic liner)
Advantages of liner material aluminium plastic
Manufacturing ++ + Permeability ++ + Cyclebility + ++ Cost for liner ++ ++ Cost for fibres + ++ Cost total + ++ Total weight + ++ Safety ++ ++
Mobile pressure vessels
Source: Funck, Handbook of Fuel Cells Vol 3, S. 83 (2003)
Stahl Komposit volume [dm³] 50 50 50 50 pressure [bar] 200 200 400 700 diameter [mm] 220 300 300 300 length [mm] 1.600 1.000 1.000 1.000 weight [kg] 70 25 45 85 stored energy [MJ] 87 87 156 238 stored energy [kWh] 24 24 43 66 stored hydrogen [kg] 0,70 0,70 1,30 2,00 grav. storage density [kWh/kg] 0,35 0,96 0,96 0,78 vol. storage density [kWh/dm³] 0,48 0,48 0,86 1,32
Mobile storage density
Source: Funck, Handbook of Fuel Cells Vol 3, S. 83 (2003)
Similarity to natural gas compression
Specific compression work (isothermal)
wt,isoth. = RH2 * T * Z * ln (p2/p1) mit RH2 = 4,124 kJ/(kg * K) = spec. Gas constant T = temperature [K] Z = (K(p1)+K(p2))/2K(p2) = compressibility factor K(p) = 1+p/150 MPa p1 = start pressure p2 = end pressure
Compressor power
P = wt,isoth. * m/t * 1/h with m/t = flux h = effective efficiency (hydraulical und mechanical losses)
Hydrogen compression
Ex. Hydrogen compression wt,isoth. for compression of 1 Nm³ H2 at 20°C from
a) 1 auf 200 bar: 6.030 kJ/kg 0,149 kWh 5,5 % b) 30 auf 200 bar: 2.179 kJ/kg 0,054 kWh 2,0 %
Eigenenergieverzehr H2-Kompression (h=85%)
0,0%
1,0%
2,0%
3,0%
4,0%
5,0%
6,0%
7,0%
8,0%
0 100 200 300 400 500 600 700 800Zieldruck [bar]
Eige
nene
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verz
ehr
Startdruck 1 barStartdruck 30 bar
1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
Source: Bünger, Wasserstoffspeicherung – Entwicklungsstand und –perspektiven, Vortrag Haus der Technik, Essen (2001)
Cryo storage
Source: www.hyweb.de
similarities to liquid helium handling
temperature at boiling point (20,4 K), pressure 1-10 bar
double wall vessel with vacuum superinsulation (70-100 layers, 25 mm) or perlite-vacuuminsulation
boil-off-rate: vacuum-superinsulation appr. 0,4 %/d vacuum-powderinsulation 1-2 %/d
Tank size: Large: NASA, Cape Canaveral, sphere with 20 m diameter, 3.800 m³ storage volume (270 t LH2), boil-off 0,03 %/d car: volume 120 dm³, passive safety by double wall hull, 100 kg total weight; heat input 2W, standby-time 4 days, boil-off-rate 1%/d
Cryo storage: data
Source: www.hyweb.de
Cryogenic process
Worldwide roughly 10 plants in operation (10 … 60 t/d each)
Small liquefiers for research purposes with 200 kg/d
Current effort: 0,9 kWhel. / dm³ LH2 (plus 45 dm³ water)
Future prospects: 0,35 kWhel. / dm³ LH2 with magnetocaloric
process
Liquefaction consumption / energy content (2,36 kWhth. / dm³ LH2) Currently 38,1 % Future 14,8 %
Hydrogen liquefaction
1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
Source: Sandrock, Handbook of Fuel Cells Vol 3, S. 101 (2003)
Metal hydrides
Base is reversible storage of hydrogen in metals:
M + ½x H2 ↔ MHx + heat
Van´t Hoffs equation:
ln p = ΔH/RT – ΔS/R (ΔH, ΔS < 0)
hydrogen loading is exothermal
hydrogen deloading is endothermal
Source: Hubert, Otto, Energiewelt Wasserstoff, TÜV Süddeutschland S. 35 (2003)
MH examples
Source: Sandrock, Handbook of Fuel Cells Vol 3, S. 101 (2003)
Activation / hydrogen loading: internal cracking increasing specific surface removing of passivation layers
Gas impurities: lead to a loss of capacity degrade kinetics poison surface
Cycle-stability is influenced by metallugic processes (disintegration)
Safety aspects: toxic, combustible
Costs: metallurgical complex process, high precision needed (200 – 700 €/Nm³ H2) used metals: La, Ti, Zr, Mg, Ca, Fe, Ni, Mn, Co, Al
MH: characteristics
Source: Sandrock, Handbook of Fuel Cells Vol 3, S. 101 (2003)
CH2 MH Dosing 0 0 Heat exchange + - Costs + - Compression - + Safety - + Weight + - Volume - + Cleaning - +
+ Advantagel 0 Equal - Disadvantage
MH vs. CH2
MH: research materials
1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
Source: Suda, Handbook of Fuel Cells Vol 3, S. 115 (2003)
Reaction: NaBH4 + 2 H2O → 4 H2 + NaBO2
Masses: 10,84 Gew.-% H2, 51,2 Gew.-% NaBH4
Reaction enthalpy: ΔH = -225 kJ/mol ~ -56 kJ/mol H2
„Hydrogen on Demand“
Pysiologic certain
Sodium borhydride
Source: Hacker, Kordesch, Handbook of Fuel Cells Vol 3, S. 121 (2003)
Reaction: 2 NH3 ↔ N2 + 3 H2
Reaction enthalpy: ΔH = 46 kJ/mol
Common chemical, worldwide logistic chain
With low pressure stored as liquid
Compared to LH2 contains ammonia the 1,7-fold amount of hydrogen (by volume)
Ammonia
Source: Hacker, Kordesch, Handbook of Fuel Cells Vol 3, S. 121 (2003)
NH3-equilibrium
Source: Hacker, Kordesch, Handbook of Fuel Cells Vol 3, S. 121 (2003)
NH3: catalytic splitting
Source: www.fuelcelltoday.de
NH3: railway application
1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
Source: Wasserstoff, Info-Blatt Messer Griesheim
Hydrogen supply options
Source: Wurster, LBST, Möglichkeiten der Wasserstoffbereitstellung, Hessischer Mobilitätstag (2003)
Hydrogen pipelines
1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
General aspects
The installation of a hydrogen infrastructure for energetic purposes is technical feasible demand-oriented („chicken-egg-problem“) expensive, but competitive to existing energy systems an economical and ecological „must do“ for the next decades
Hardware is proved in R&D-projects, and the design and erection phase is object of studies. More details:
http://www.h2hamburg.de/downloads/MBA_HH%20H2.pdf http://www.iea.org/work/2007/hydrogen_economy/modelling_seydel.pdf
1. Hydrogen storage a) gaseous b) liquid c) physically bound d) chemically bound
2. Hydrogen distribution
3. Hydrogen infrastructure
4. Summary
Structure
Summary
The installation of a hydrogen infrastructure for energetic purposes is oriented on solutions for the chemical industry. They offer tailored storage and distribution hardware for each demand. The installation of a hydrogen infrastructure for energetic purposes seems to be expensive, but their cost is within the range of existing energy solutions. The installation of a hydrogen infrastructure for energetic purposes will develop within the next decades from local to regional networks.